6,7-dihydro-pyrazolo (1,5-A)(1,3,5)triazine-2-sulphonamides, processes for their preparation and their use as herbicides and plant growth regulators

ABSTRACT

The invention relates to new 6,7-dihydropyrazole-[1,5-a][1,3,5]triazine-2-sulphonamides of general formula I   &lt;IMAGE&gt; (I)  in which Ar, R6, R7, R8, R9 and X have the meanings given in the description, processes for their preparation and their use as herbicides and plant growth regulants.

The invention relates to new6,7-dihydropyrazolo-[1,5-a][1,3,5]triazine-2-sulphonamides, processesfor their preparation and their use as herbicides and plant growthregulators.

It is known that triazolopyrimidinesulphonamides possess herbicidalactivity (EP 142 152 and 150 974). However the herbicidal activity ofthe known compounds is not sufficient and/or selectivity problems canoccur in important crops.

The object of the present invention is to make new compounds that do notshow the disadvantages of the known compounds and have improvedbiological properties.

It has now been found that6,7-dihydropyrazolo-[1,5-a][1,3,5]triazine-2-sulphonamides of generalformula I ##STR2## in which Ar is a phenyl, naphthyl, pyridyl or thienylgroup of general formula ##STR3##

R₁, R₂, R₃, R₄ and R₅ are the same or different and are hydrogen, a C₁-C₆ -alkyl, C₂ -C₆ -alkenyl or C₂ -C₆ -alkynyl group, each of which isoptionally substituted by one or more of the same or different halo,hydroxy, halo-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halo-C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, halogen,C₁ -C₄ -alkoxy, a group R_(10--O--CO), a carbamoyl group R₁₁ R₁₂N--CO--, an amino group R₁₁ R₁₂ N--, cyano, nitro, a sulphur containinggroup R₁₀ --S(O)_(n) --, an acyl group R₁₀ --CO, a group R₁₀--O--CO--(CH₂)_(n), or phenyl or phenoxy, both of which are optionallysubstituted by one or more of C₁ -C₄ -alkyl, halo or nitro,

R₆ is hydrogen, an acyl group R₁₀ --CO, a group R₁₀ --O--CO--, C₁ -C₆-alkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkynyl, phenyl-C₁ -C₄ -alkyl, acarbamoyl group R₁₁ R₁₂ N--CO--, an alkali metal atom, a single metalequivalent of an alkaline earth or other metals or ammonium group,optionally substituted by C₁ -C₆ -alkyl,

R₇ and R₈ are the same or different and are hydrogen, a C₁ -C₆ -alkyl,C₂ -C₆ -alkenyl or C₂ -C₆ -alkynyl group, each of which is optionallysubstituted by halo and/or C₁ -C₄ -alkoxy, a phenyl-C₁ -C₆ -alkyl,phenyl-C₂ -C₆ -alkenyl or phenyl-C₂ -C₆ -alkynyl group, each of which isoptionally substituted by halo, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl or halo-C₁ -C₄ -alkyl, phenyl, substituted by R₁,R₂, R₃, R₄ and R₅, an acyl group R₁₀ --CO, a group R₁₀ --O--CO, a groupR₁₀ --O--CO--(CH₂)_(n), a carbamoyl group R₁₁ R₁₂ N--CO--, or asulphonyl group R₁₀ --SO₂,

R₉ is hydrogen, a C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl or C₂ -C₆ -alkynylgroup, each of which is optionally substituted by halo and/or C₁ -C₄-alkoxy, a phenyl-C₁ -C₆ -alkyl, phenyl-C₂ -C₆ -alkenyl or phenyl-C₂ -C₆-alkynyl group, each of which is optionally substituted by halo, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl or halo-C₁ -C₄-alkyl, phenyl, substituted by R₁, R₂, R₃, R₄ and R₅, an acyl group R₁₀--CO, a group R₁₀ --O--CO, a group R₁₀ --O--CO--(CH₂)_(n), a carbamoylgroup R₁₁ R₁₂ N--CO--, a sulphonyl group R₁₀ --SO₂ or R₁₀ --O--SO₂,cyano or nitro

R₁₀ is hydrogen, a C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkynyl orphenyl-C₁ -C₄ -alkyl group, each of which is optionally substituted byone or more of the same or different halo, hydroxy or C₁ -C₄ -alkoxy, orphenyl, optionally substituted by halo, nitro or C₁ -C₄ -alkyl,

R₁₁ and R₁₂ are the same or different and are hydrogen, a C₁ -C₆ -alkyl,C₂ -C₆ -alkenyl or C₂ -C₆ -alkynyl group, each of which is optionallysubstituted by one or more of the same or different halo, hydroxy or C₁-C₄ -alkoxy, or

R₁₁ and R₁₂ together with the adjacent nitrogen form a pyrrolidinyl,piperidino or morpholino ring,

X is oxygen or sulphur, and

n is 0, 1 or 2, show an interesting herbicidal and plant growth regulantactivity.

The term "halogen" in relationship with alkyl, alkenyl, alkynyl orphenyl means that one or more hydrogen atoms are replaced by one or morehalogen atoms.

The term "halogen" means fluorine, chlorine, bromine and iodine.

6,7-Dihydropyrazolo[1,5-a][1,3,5]triazine-2-sulphonamides of generalformula I which show particularly good activity are those in which

Ar is a phenyl group of general formula ##STR4##

R₁ and R₅ are the same or different and are halogen, methyl,trifluoromethyl, nitro, methoxy or methoxycarbonyl,

R₂, R₃ and R₄ are the same or different and are hydrogen, halogen,trifluoromethyl or a C₁ -C₄ -alkyl group,

R₆ is hydrogen, a single equivalent of a metal or a C₁ -C₄ -acyl group,

R₇ and R₈ are the same or different and are hydrogen, C₁ -C₄ -acyl, C₁-C₆ -alkyl, C₂ -C₄ -alkenyl or phenyl, and

R₉ is hydrogen, a C₁ -C₄ -acyl group, a group R₁₀ --O--CO, a carbamoylgroup R₁₁ R₁₂ N--CO--, a sulphonyl group R₁₀ --SO₂, cyano or nitro.

The compounds of the invention of general formula I can be prepared forexample by

(A) reacting an amine of general formula II,

    Ar--NH--R.sub.6                                            (II)

in which Ar has the meaning given above and R₆ is hydrogen, C₁ -C₆-alkyl, C₂ -C₆ -alkenyl or C₂ -C₆ -alkynyl, with a sulphonyl chloride ofgeneral formula III ##STR5## in which R₇, R₈, R₉ and X have the meaningsgiven above in a suitable solvent and in the presence of an acidacceptor, or

(B) reacting a compound of general formula IV ##STR6## in which Ar andR₉ have the meaning given above and R₆ is hydrogen, C₁ -C₆ -acyl, C₂ -C₆-alkenyl or C₂ -C₆ -alkynyl, with an isocyanate or isothiocyanate offormula V

    R.sub.7 --NCX                                              (V)

in which R₇ and X have the meanings given above in a suitable solvent,optionally in the presence of an acid acceptor and/or catalyst, andreacting the resulting compound of general formula VI ##STR7## in whichAr, R₇, R₉ and X have the meanings given above and R₆ is hydrogen, C₁-C₆ -alkyl, C₂ -C₆ -alkenyl or C₂ -C₆ -alkynyl, with an ortho ester ofgeneral formula VII

    R.sub.8 --C(OR.sub.10).sub.3                               (VII)

in which R₁₀ has the meaning given above, except hydrogen, and R₈ ishydrogen, a C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl or C₂ -C₆ -alkynyl group,each of which is optionally substituted by halo and/or C₁ -C₄ -alkoxy, aphenyl-C₁ -C₆ -alkyl, phenyl-C₂ -C₆ -alkenyl or phenyl-C₂ -C₆ -alkynylgroup, each of which is optionally substituted by halo, C₁ -C₄ -alkyl,C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl or halo-C₁ -C₄ -alkyl, orphenyl, substituted by R₁, R₂, R₃, R₄ and R₅, in a suitable solvent,which can be the orthoester itself, or

(C) reacting a compound of general formula IV ##STR8## in which Ar andR₉ have the meaning given above and R₆ has the meaning given under (B),with an ortho ester of general formula VII

    R.sub.8 --C(OR.sub.10).sub.3                               (VII)

in which R₈ and R₁₀ have the meanings given under (B), in a suitablesolvent, which can be the orthoester itself, to give a compound offormula VIII ##STR9## which is reacted with an isocyanate orisothiocyanate of formula V

    R.sub.7 --NCX                                              (V)

in which R₇ and X have the meanings given above in a suitable solvent,optionally in the presence of an acid acceptor and/or catalyst, or

(D) reacting a compound of general formula IX ##STR10## in which Ar, R₇,R₈, R₉ and X have the meanings given above and R₁₃ is hydrogen or asingle equivalent of a metal, with a compound of general formula X

    R.sub.10 --Hal                                             (X)

or of general formula XI

    R.sub.10 --CO--Hal                                         (XI)

in which R₁₀ has the meaning given above, except hydrogen and Hal ischlorine or bromine, or of general formula XII

    R.sub.10 --CO--O--COR.sub.10                               (XII)

in which R₁₀ has the meaning given above, in a suitable solvent, or

(E) reacting a compound of general formula XIII ##STR11## in which Ar,R₇, R₈, R₉ and X have the meanings given above, with a compound ofgeneral formula XIV

    M--Y                                                       (XIV)

in which M is a single equivalent of a metal, and Y is hydrogen,hydroxy, lower alkyl, lower alkoxy or an amino group, in a suitablesolvent.

The particular reaction variants are preferably carried out in thepresence of a diluent. For this purpose there are used solvents whichare inert to the reactants.

Examples of such solvents or diluents are water, aliphatic, alicyclicand aromatic hydrocarbons, that can optionally be chlorinated, such asfor example hexane, cyclohexane, petroleum ether, ligroin, benzene,toluene, methylene chloride, chloroform, carbon tetrachloride, ethylenedichloride and trichloroethane, ethers, such as for example diisopropylether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran,ketones such as for example acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, nitriles, such as forexample acetonitrile and propionitrile, alcohols, such as for examplemethanol, ethanol, isopropanol, butanol and ethylene glycol, esters,such as for example ethyl acetate and amyl acetate, amides, such as forexample dimethylformamide and dimethylacetamide, sulphones andsulphoxides, such as for example dimethyl sulphoxide and and sulpholane,and bases, such as for example pyridine.

The reaction is suitably carried out between room temperature and theboiling point of the particular reaction mixture. The reaction can becarried out under atmospheric pressure but if desired higher or lowerpressures can be used.

Process variant A is preferably carried out in chlorinated hydrocarbons,such as dichloromethane or dichloroethane, in the presence of a catalystand and/or acid acceptor. Examples of these are tertiary amines such asfor example triethylamine, diisopropylethylamine, N-methylmorpholine,4-dimethylaminopyridine and pyridine. Pyridine can be used both ascatalyst and as a solvent.

Process variants B and C are preferably carried out in diluents such as,aliphatic, alicyclic and aromatic hydrocarbons, that can optionally bechlorinated, such as for example hexane, cyclohexane, petroleum ether,ligroin, benzene, toluene, methylene chloride, chloroform, carbontetrachloride, ethylene dichloride and trichloroethane, ethers, such asfor example diisopropyl ether, dibutyl ether, propylene oxide, dioxaneand tetrahydrofuran, ketones such as for example acetone, methyl ethylketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles,such as for example acetonitrile and propionitrile, esters, such as forexample ethyl acetate and amyl acetate, amide, such as for exampledimethylformamide and dimethylacetamide, sulphones and sulphoxides, suchas for example dimethyl sulphoxide and and sulpholane, and bases, suchas for example pyridine, and optionally in the presence of a catalystand and/or acid acceptor. Examples of these are tertiary amines such asfor example triethylamine, diisopropylethylamine, N-methylmorpholine,4-dimethylaminopyridine and pyridine.

Process variant D is preferably carried out by reacting a compound ofgeneral formula IX in a suitable solvent with a compound of generalformula X, XI or XII, filtering off the salts which as general rule arehighly insoluble and recovering the desired compounds after evaporationof the solvent.

Process variant E is preferably carried out by reacting a compound ofgeneral formula XIII in a suitable solvent with a metal base, such as ametal hydroxide, metal hydride, metal alkyl or metal amide, and thesalts which as a general rule are highly insoluble can be recovered byfiltration or by evaporation of the solvent.

The compounds of the invention prepared by these processes can beisolated from the reaction mixtures in conventional manner, for exampleby distillation of the solvent at normal or reduced poressure, byprecipitation with water or by extraction.

A higher level of purity can be achieved as a rule by columnchromatography as well as by fractional distillation or crystallisation.

The compounds of the invention are, as a rule, colorless or odourlesscrystals that are slightly soluble in water and in aliphatichydrocarbons such as petroleum ether, hexane, pentane and cyclohexaneand highly soluble in halogenated hydrocarbons, such as chloroform,methylene chloride and carbon tetrachloride, aromatic hydrocarbons suchas benzene, toluene and xylene, ethers, such as diethyl ether,tetrahydrofuran and dioxane, nitriles, such as acetonitrile, alcohols,such as methanol and ethanol, amides, such as dimethylformamide, andsulphoxides, such as dimethyl sulphoxide.

The sulphonyl chlorides of general formula III are new and can beprepared as described in the literature or by known methods by reactinga 2-benzylthio-6,7-dihydropyrazolo[1,5-a][1,3,5]triazin-7-one of generalformula XV ##STR12## in which R₇, R₈, R₉ and X have the meanings givenabove, with chlorine in water or a water/acetic acid mixture.

Amines of general formula II, isocyanates and isothiocyanates of generalformula V and orthoesters of general formula VII are in the maincommercially available or can be prepared by known processes or asdescribed in the literature.

The compounds of the invention influence plant growth and can thereforebe used as plant growth regulators and especially as herbicides.Surprisingly, the compounds of the invention show a wide activityagainst monocotyledonous and dicotyledonous weeds with good selectivityin crops. Whether the compounds of the invention act as total orselective herbicides depends mainly on the rates of use but also on thespecies and the time of use.

The compounds can be used in seed treatments, and in pre or postemergent use.

The compounds of the invention can used for example against thefollowing plant species:

Dicotyledonous weeds of the species Polygonum, Sinapis, Atriplex,Spergula, Stellaria, Galium, Viola, Cirsium, Amaranthus, Ipomoea,Xanthium, Abutilon, Chenopodium, Cassia, convolvulus, Mentha, Veronica,Matricaria, Solanum, Lamium, Thlapsi, Capsella, Datura, Galinsoga,Mercurialis, Rhaphanus, Vicia, Portulaca, Physalis, Sida, Anoda,Euphorbia, Myosotis, Centaurea, Brassica, Chrysanthemum and Helianthus;

Monocotyledonous weeds of the species Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis,Alopecurus, Apera, Rottoboellia, Triticum and Hordeum.

The compounds can be used in important agricultural crops, such aswheat, barley, rice and cotton.

The use of the compounds of the invention is not limited to the weedsand crops mentioned above but can also be applied in a similar way toother plants.

The compounds are also suitable for weed control in industrial andrailway installations and also roads and verges, with or withoutvegetation, in forests, woodlands, berry fruit and hop installations, aswell as plantations.

The rates of use can vary over a wide range. They depend generally onthe nature of the desired effects. In general the rates of use liebetween 0.01 and 5 kg of active ingredient per hectare and preferablyfor example in weed control between 0.1 and 0.5 kg of active ingredientper hectare.

The compounds of the invention can be used either alone or in admixturewith one another or with other active agents. Optionally, otherplant-protective agents or pesticides can be added, depending on thepurpose for the treatment. When it is desired to broaden the spectrum ofactivity, other herbicides can also be added. Herbicidally active mixingpartners suitable in this connection include for example, the activeagents listed in Weed Abstracts, vol. 34, No. 5 (1986) under the heading"Lists of common names and abbreviations employed for currently usedherbicides and plant growth regulators in Weed Abstracts".

An improvement in the intensity and speed of action can be obtained, forexample, by addition of suitable adjuvants, such as organic solvents,wetting agents and oils. Such additives may allow a decrease in thedose.

Suitable mixture partners may include phospholipids, e.g.phosphatidylcholine, hydrated phosphatidylcholinesphosphatidylethanolamine, N-acyl-phosphatidylethanolamines,phosphatidylinositol, phosphatidylserine, lysolecithin orphosphatidylglycerol.

The designated active ingredients or their mixtures can suitable beused, for example, as powders, dusts, granules, solutions, emulsions orsuspensions, with the addition of liquid and/or solid carriers and/ordiluents and, optionally, binding, wetting emulsifying and/or dispersingadjuvants.

Suitable liquid carriers are, for example aliphatic and aromatichydrocarbons, such as benzene, toluene, xylene, cyclohexanone,isophorone, dimethyl sulphoxide, dimethylformamide and other mineral-oilfractions and plant oils.

Suitable solid carriers include mineral earths, e.g. bentonite, silicagel, talcum, kaolin, attapulgite, limestone, silicic acid and plantproducts, e.g. flours.

As surface-active agents there can be used for example calciumlignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonicacids and their salts, phenolsulphonic acids and their salts,formaldehyde condensates, fatty alcohol sulphates, as well assubstituted benzenesulphonic acids and their salts.

The percentage of the active ingredient(s) in the various preparationscan vary within wide limits. For example, the compositions can containabout 10 to 90 percent by weight active ingredients, and about 90 to 10percent by weight liquid or solid carriers, as well as, optionally up to20 percent by weight of surfactant.

The agents can be applied in customary fashion, for example with wateras the carrier in spray mixture volumes of approximately 100 to 1,000l/ha. The agents can be applied using low-volume or ultra-low-volumetechniques or in the form of so-called microgranules.

The preparation of these formulations can be carried out in knownmanner, for example by milling or mixing processes. Optionally,individual components can be mixed just before use for example by theso-called commonly used tank-mixing method.

Formulations can be prepared, for example, from the followingingredients.

(A) Wettable Powder

(1) 25 percent by weight active ingredient

60 percent by weight kaolin

10 percent by weight silicic acid

5 percent by weight of a mixture of calcium lignosulphonate and thesodium salt of N-methyl-N-oleyltaurine

(2) 40 percent by weight active ingredient

25 percent by weight bentonite

25 percent by weight colloidal silicic acid

10 percent by weight of a mixture of calcium lignosulphonate andalkylphenyl polyglycol ether

(B) Paste

45 percent by weight active ingredient

5 percent by weight sodium aluminium silicate

15 percent by weight cetyl polyglycol ether with 8 mol of ethylene oxide

2 percent by weight spindle oil

10 percent by weight polyethylene glycol

23 percent by weight water

(C) Emulsifiable Concentrate

25 percent by weight active ingredient

15 percent by weight cyclohexanone

55 percent by weight xylene

5 percent by weight of a mixture of calcium dodecylbenzenesulphonate andnonylphenolpolyoxyethylene.

The following examples illustrate the preparation of compound accordingto the invention.

EXAMPLE 1N-(2,6-Dichlorophenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide(process A)

2.84 g (17.5 mmol) 2,6-Dichloroaniline was stirred in 15 ml pyridinewith 5.00 g (15.6 mmol)6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo[1,5-a][1,3,5]-triazine-2-sulphonylchloride for 15 hours at 50° C. and the undissolved residue filtered.The filtrate was concentrated, the residue treated with 2N sulphuricacid, the product suction filtered, chromatographed with hexane/ethylacetate over silica gel and recrystallised from ethyl acetate.

Yield: 1.97 g=28% of theory.

M.p.: 265°-267° C.

Elementary analysis

Calc. (%): C 40.37 H 2.94 N 15.69 S 7.19 Cl 15.89. Found (%): C 40.45 H3.34 N 14.94 S 7.21 Cl 15.70.

Preparation of the starting material for Example 1 (a)6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonylchloride

15.50 g (43 mmol)2-Benzylthio-6,7-dihydro-3-methoxycarbonyl-5,6-dimethyl-7-oxopyrazolo[1,5-a][1,3,5]triazine-7-thionewas suspended in 200 ml water/acetic acid (1:1 mixture). At 10° C.,chlorine was introduced over 3 hours. The product was extracted withmethylene chloride and dried over magnesium sulphate. Afterconcentrating, the residue was treated with ether and the productsuction filtered.

Yield: 9.70 g=70% of theory.

M.p.: 188°-190° C.

(b)2-Benzylthio-6,7-dihydro-3-methoxycarbonyl-5,6-dimethyl-7-oxopyrazolo[1,5-a][1,3,5]triazine-7-thione

6.77 g (20.1 mmol) 5-Amino-B3-benzylthio-4-methoxycarbonyl-N-methylpyrazole-1-carbothioamide wasstirred in 35 ml triethyl orthoacetate allowing the ethanol which formedto distil off. After cooling, the product was suction filtered, washedwith ether and dried.

Yield: 5.35 g=74% of theory.

M.p.: 212°-213° C.

Elementary analysis Calc. (%): C 53.51 H 4.47 N 15.54 S 17.79. Found(%): C 53.37 H 4.27 N 15.56 S 18.11.

(c)5-Amino-3-benzylthio-4-methoxycarbonyl-N-methylpyrazole-1-carbothioamide

45.11 g (0.127 mol) Methyl 3,3-dibenzylthio-2-cyanoacrylate and 13.35 g(0.127 mol) 4-methylthiosemicarbazide in 225 ml ethanol were heatedunder reflux for 10 hours. After cooling, the product was suctionfiltered, washed with ether and dried.

Yield: 33.61 g=79% of theory.

M.p.: 162°-163° C.

Elementary analysis Calc. (%): C 49.98 H 4.79 N 16.65 S 19.06. Found(%): C 50.00 H 5.12 N 16.78 S 19.48.

(d) Methyl 3,3-dibenzylthio-2-cyanoacrylate

A solution of sodium methanolate was prepared from from 80.49 g (3.5mol) sodium and 1050 ml methanol. 200.2 g (2.0 mol) of 99% methyl2-cyanoacrylate was dissoved on 600 ml of this solution, the mixturecooled to 5° C. and 60 ml (1.0 mol) carbon disulphide added, dropwise,under cooling. A further 300 ml of the methanolate solution was addedand the mixture cooled to 10° C. 30 ml (0.5 mol) Carbon disulphide wasadded dropwise, after which the remaining methanolate solution wasadded, and finally a further 15.75 ml (0.25 mol) carbon disulphide wasadded, dropwise. The mixture was stirred for 30 minutes at 15° C. 598.68g (3.5 mol) Benzyl bromide was added dropwise, with cooling. The mixturewas stirred for 2 hours at 20° C., the solvent distilled and the residuetreated with ice-water. The product was suction filtered, washed withwater and ether and dried.

Yield: 521.2 g=84% of theory.

M.p.: 100°-101° C.

Elementary analysis Calc. (%): C 64.19 H 4.82 N 3.94 S 18.04. Found (%):C 64.14 H 4.82 N 4.18 S 17.82.

EXAMPLE 2N-(2,6-Difluorophenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-thioxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide(process C)

2.6 g (6.7 mmol)N-(2,6-difluorophenyl)-4-methoxycarbonyl-5-(1-methoxyethylidenamino)pyrazole-3-sulphonamidewas stirred with 20 ml tetrahydrofuran, 0.88 ml (12 mmol) methylisothiocyanate and 0.71 ml (7 mmol) triethylamine for 8 hours at 50° C.The mixture was cooled to 5° C., the crystals suction filtered andwashed with tetrahydrofuran and ether.

Yield: 1.5 g=52% of theory.

M.p.: 284°-286° C.

Elementary analysis Calc. (%): C 41.95 H 3.05 N 16.31 S 14.93 F 8.85.Found (%): C 41.89 H 3.49 N 16.23 S 15.09 F 8.91.

Preparation of the starting material for Example 2 (a)N-(2,6-Difluorophenyl)-4-methoxycarbonyl-5-(1-methoxyethylidenamino)pyrazole-3-sulphonamide

5.0 g (15mmol)5-amino-N-(2,6-difluorophenyl)-4-methoxycarbonylpyrazole-3-sulphonamidewas heated under reflux with 50 ml acetonitrile, 2.1 ml (17.5 mmol)triethyl orthoacetate and 3 drops acetic acid for 8 hours. Theundissolved residue was filtered and the filtrate concentrated. Theresidue was chromatographed with hexane/ethyl acetate over silica geland recrystallised from ether.

Yield: 4.8 g=82% of theory.

M.p.: 194°-196° C.

Elementary analysis Calc. (%): C 43.30 H 3.63 N 14.43 S 8.26 F 9.78.Found (%): C 43.27 H 3.98 N 14.13 S 8.09 F 9.69.

(b)5-Amino-N-(2,6-difluorophenyl)-4-methoxycarbonylpyrazole-3-sulphonamide

7.50 g (20 mmol)5-acetamido-N-(2,6-difluorophenyl)-4-methoxycarbonylpyrazole-3-sulphonamidewas suspended in 80 ml 4.4N methanolic hydrochloric acid and heatedunder reflux for 5 hours. The solvent was distilled and the residuetreated with water. The product was suction filtered, washed with waterand dried.

Yield: 6.2 g=93% of theory.

M.p.: 265°-266° C.

Elementary analysis Calc. (%): C 39.76 H 3.03 N 16.86 S 9.65 F 11.44.Found (%): C 40.23 H 3.25 N 17.12 S 9.80 F 11.46.

(c)5-Acetamido-N-(2,6-difluorophenyl)-4-methoxycarbonylpyrazole-3-sulphonamide

23.63 g (177.5 mmol) of 97% 2,6-difluoroaniline and 1.48 gN,N-dimethyl-4-aminopyridine was dissolved in 225 ml pyridine and 25.0 g(88.75 mmol) 5-acetamido-4-methoxycarbonylpyrazole-3-sulphonyl chlorideadded portionwise. The mixture was stirred for 48 hours at 25° C. Thepyridine was distilled and the residue dissolved in 510 ml methylenechloride washed twice with 370 ml 5N hydrochloric acid and twice with370 ml water, dried over magnesium sulphate and concentrated. Theresidue was triturated with ether, the product suction filtered, washedwith ether and dried.

Yield: 17.53 g=53% of theory.

M.p.: 221°-222° C.

Elementary analysis Calc. (%): C 41.71 H 3.23 N 14.97 S 8.57 F 10.15.Found (%): C 41.66 H 3.30 N 14.83 S 8.54 F 10.23.

(d) 5-Acetamido-4-methoxycarbonylpyrazole-3-sulphonyl chloride

73.0 g (239 mmol) Methyl 5-acetamido-3-benzylthiopyrazole-4-carboxylatewas dissolved in 470 ml methylene chloride and treated with 124.15 gsilica gel and 25.6 g water and cooled to 0° C. 160.6 g (1.19 mol)Sulphuryl chloride in 730 ml methylene chloride was added dropwise. Themixture was stirred for 3 hours at 0° C., filtered, washed several timeswith methylene chloride, dried over magnesium sulphate and concentrated.The residue was triturated with ether/hexane, the crystals suctionfiltered, washed with hexane and dried.

Yield: 51.9 g=77% of theory.

M.p.: 143°-144° C.

Elementary analysis Calc. (%): C 29.85 H 2.86 N 14.92 S 11.38 F 12.59.Found (%): C 29.92 H 2.76 N 14.87 S 11.40 F 12.51.

(e) Methyl 5-acetamido-3-benzylthiopyrazole-4-carboxylate

70.5 g (0.27 mol) Methyl 5-amino-3-benzylthiopyrazole-4-carboxylate wasdissolved at 80° C. in 135 ml glacial acetic acid and treated with 27.75g (0.27 mol) acetic anhydride. The solution was heated under reflux for7 hours and concentrated. The residue was recrystallised from ether, thecrystals suction filtered, washed with ether and dried.

Yield: 73.2 g=89% theory.

M.p.: 136°-137° C.

Elementary analysis Calc. (%): C 55.07 H 4.95 N 13.76 S 10.50. Found(%): C 55.17 H 4.77 N 13.80 S 10.79.

(f) Methyl 5-amino-3-benzylthiopyrazole-4-carboxylate

124.34 g (0.35 mol) Methyl 3,3-dibenzylthio-2-cyanoacrylate and 46.70 g(0.35 mol) t-butyl hydrazinoformate was heated under reflux for 3.5hours in 700 ml ethanol and concentrated. The residue was treated with700 ml glacial acetic acid and stirred for 3 hours at 110° C. and for 1hour at 5° C. The product was suction filtered, washed with glacialacetic acid and hexane and dried.

Yield: 70.9 g=77% of theory.

M.p.: 111°-112° C.

Elementary analysis Calc. (%): C 54.73 H 4.97 N 15.96. Found (%): C54.02 H 4.68 N 15.93.

EXAMPLE 3N-(2,6-Difluorophenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide(process C)

1.5 g (3.9 mmol)N-(2,6-difluorophenyl)-4-methoxycarbonyl-5-(1-methoxyethylidenamino)pyrazole-3-sulphonamidewas stirred with 20 ml tetrahydrofuran, 0.29 g (5.0 mmol) methylisocyanate and 0.39 ml (3.9 mmol) triethylamine for 48 hours at 25° C.The crystals were suction filtered and washed with tetrahydrofuran andether.

Yield: 1.3 g=81% of theory.

M.p.: 257°-259° C.

Elementary analysis Calc. (%): C 43.58 H 3.17 N 16.94 S 7.76 F 9.19.Found (%): C 43.34 H 3.23 N 16.80 s 7.53 F 9.03.

In a similar manner to Examples 1 to 3 the following compounds of theinvention were prepared were prepared.

    ______________________________________                                        Ex-                                                                           am-                                                                           ple                             Physical                                      No   Name of Compound           Constant                                      ______________________________________                                        4    N--(2,6-Dichlorophenyl)-6,7-dihydro-                                                                     mp:304-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 305° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            5    N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-                                                            mp:262-                                            5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                                                    264° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            6    N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-                                                            mp:312-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 314° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            7    N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-                                                                mp:240-                                            5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                                                    242° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            8    N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-                                                                mp:285-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 286° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            9    N--(2-Chloro-6-methylphenyl)-6,7-dihydro-                                                                mp:259-                                            5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                                                    261° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            10   N--(2-Chloro-6-methylphenyl)-6,7-dihydro-                                                                mp:295-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 297° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            11   N--(2,6-Dibromophenyl)-6,7-dihydro-                                                                      mp:293-                                            5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                                                    295° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            12   N--(2,6-Dibromophenyl)-6,7-dihydro-                                                                      mp:327-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 330° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            13   N--(2-Methyl-6-nitrophenyl)-6,7-dihydro-                                                                 mp:230-                                            5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                                                    232° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide.                                hydrate                                                                  14   N--(2-Methyl-6-nitrophenyl)-6,7-dihydro-                                                                 mp:271-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 274° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            15   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                                              mp:210-                                            N--(2-methoxycarbonyl-6-methylphenyl)-7-thiox-                                                           212° C.                                     o-pyrazol[1,5-a][1,3,5]triazine-2-sulphonamide                           16   N--(2-Bromo-6-methoxyphenyl)-6,7-dihydro-                                                                mp:276-                                            5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                                                 278° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide,                                x hydrate                                                                17   N--(2,6-Dichlorophenyl)-6,7-dihydro-                                                                     mp:283-                                            5,6-dimethyl-3-ethoxycarbonyl-7-oxo-                                                                     284° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            18   N--(2,6-Difluorophenyl)-6,7-dihydro-                                                                     mp:221-                                            5,6-dimethyl-3-ethoxycarbonyl-7-oxo-                                                                     223° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            19   N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-                                                                mp:214-                                            5,6-dimethyl-3 ethoxycarbonyl-7-oxo-                                                                     217° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            20   N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-                                                            mp:228-                                            5,6-dimethyl-3-ethoxycarbonyl-7-oxo-                                                                     230° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            21   N--(2,6-Dibromophenyl)-6,7-dihydro-                                                                      mp:295-                                            5,6-dimethyl-3-ethoxycarbonyl-7-oxo-                                                                     297° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            22   N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-                                                                 mp:285-                                            5,6-dimethyl-3-ethoxycarbonyl-7-oxo-                                                                     286° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            23   N--(2,6-Dichlorophenyl)-6,7-dihydro-                                                                     mp:272-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  274° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            24   6,7-Dihydro-5,6-dimethyl-3-ethoxycarbonyl-                                                               mp:182-                                            N--(2-methoxycarbonyl-6-methyphenyl)-7-thioxo-                                                           186° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            25   N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-                                                            mp:257-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  259° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            26   N--(2-Chloro-6-fluorophenyl)-6,7-dihydro-                                                                mp:232-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  235° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            27   N--(2,6-Difluorophenyl)-6,7-dihydro-                                                                     mp:214-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  216° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            28   N--(2-Chloro-6-methylphenyl)-6,7-dihydro-                                                                mp:225-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  226° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            29   N--(2,6-Dibromophenyl)-6,7-dihydro-                                                                      mp:285-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  287° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            30   N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-                                                                 mp:291-                                            5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  293° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            31   3-Cyano-N--(2,6-dichlorophenyl)-6,7-dihydro-                                                             mp:338-                                            5,6-dimethyl-7-oxopyrazolo-                                                                              341° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    32   3-Cyano-N--(2,6-dibromophenyl)-6,7-dihydro-                                                              mp:                                                5,6-dimethyl-7-oxopyrazolo-                                                                              303 (dec)                                          [1,5-a][1,3,5]triazine-2-sulphonamide                                    33   3-Cyano-N--(2,6-dichloro-3-methylphenyl)-                                                                mp:298-                                            6,7-dihydro-5,6-dimethyl-7-oxopyrazolo                                                                   303° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    34   3-Cyano-6,7-dihydro-5,6-dimethyl-                                                                        mp:258-                                            N--(2-methoxycarbonyl-6-methylphenyl)-7-oxo-                                                             262° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            35   3-Cyano-N--(2,6-dichlorophenyl)-6,7-dihydro-                                                             mp:279-                                            5,6-dimethyl-7-thioxopyrazolo-                                                                           282° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    36   3-Cyano-N--(2,6-dichloro-3-methylphenyl)-                                                                mp:272-                                            6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-                                                               273° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    37   3-Cyano-N--(2,6-dibromophenyl)-6,7-dihydro-                                                              mp:300°                                     5,6-dimethyl-7-thioxopyrazolo-                                                                           C. (dec)                                           [1,5-a][1,3,5]triazine-2-sulphonamide                                    38   3-Cyano-6,7-dihydro-5,6-dimethyl-                                                                        mp:248-                                            N--(2-methoxycarbonyl-6-methylphenyl)-7-thioxo-                                                          249° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            39   3-Carbamoyl-N--(2,6-dichlorophenyl)-                                                                     mp:303-                                            6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-                                                                  305° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    40   3-Carbamoyl-N--(2,6-dichloro-3-methylphenyl)-                                                            mp:307°                                     6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-                                                                  C. (dec)                                           [1,5-a][1,3,5]triazine-2-sulphonamide                                    41   3-Carbamoyl-N--(2,6-dibromophenyl)-                                                                      mp:274-                                            6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-                                                                  275° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    42   3-Carbamoyl-N--(2,6-dichlorophenyl)-                                                                     mp:295-                                            6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-                                                               296° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    43   3-Carbamoyl-N--(2,6-dichloro-3-methylphenyl)-                                                            mp:269°                                     6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-                                                               C. (dec)                                           [1,5-a][1,3,5]triazine-2-sulphonamide                                    44   3-Carbamoyl-N--(2,6-dibromophenyl)-                                                                      mp:279-                                            6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-                                                               280° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    45   N--(2,6-Dichlorophenyl)-6,7-dihydro-                                                                     mp:289-                                            5,6-dimethyl-3-methylsulphonyl-7-oxopyrazolo-                                                            292° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    46   N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-                                                            mp:273-                                            5,6-dimethyl-3-methylsulphonyl-7-oxopyrazolo-                                                            275° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    47   N--(2,6-Dichlorophenyl)-6,7-dihydro-                                                                     mp:318-                                            5,6-dimethyl-3-methylsulphonyl-7-thioxo-                                                                 320° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            48   N--(2,6-Dichloro-3-methylphenyl)-6,7-dihydro-                                                            mp:290-                                            5,6-dimethyl-3-methylsulphonyl-7-thioxo-                                                                 293° C.                                     pyrazolo[ 1,5-a][1,3,5]triazine-2-sulphonamide                           49   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   N--(2-methoxycarbonyl-6-methylphenyl)-7-oxo-                                  pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            50   N--(2-Bromo-6-methoxyphenyl)-6,7-dihydro-                                     5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                         pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            51   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   7-oxo-N--(2-trifluoromethylphenyl)-                                           pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            52   6,7-Dihydro-5,6-dimethyl-N--(5,6-dimethyl-                                    2-nitrophenyl)-3-methoxycarbonyl-7-oxo                                        pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            53   N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-                                      5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                         pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            54   N--(2-Bromo-6-chloro-3-methylphenyl)-                                         6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-                                 oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                         55   N--(2-Bromo-6-chloro-5-methylphenyl)-                                         6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-                                 oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                         56   N--(2,6-Dibromo-3-methylphenyl)-6,7-dihydro-                                  5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                         pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            57   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl                                    N--(6-methyl-2-trifluoromethylphenyl)-7-oxo-                                  pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            58   N--(2-Difluoromethoxy-6-methylphenyl)-                                        6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-7-                                 oxopyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                         59   6,7-Dihydro-5,6-dimethyl-N--(3,6-dimethyl-                                    2-nitrophenyl)-3-methoxycarbonyl-7-oxo-                                       pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            60   N--[2,6-Bis(difluoromethoxyphenyl)]6-Bis(difluoromethoxyphenyl)]-6,7-         dihydro-                                                                      5,6-dimethyl-3-methoxycarbonyl-7-oxo-                                         pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            61   6,7-Dihydro-5,6-dimethyl-N--(6-fluoro-                                        2-methoxycarbonyl-3-methylphenyl)-3-methoxy-                                  carbonyl-7-oxo-pyrazolo[1,5-a][1,3,5]triazine-                                2-sulphonamide                                                           62   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   N--(2-methoxy-6-trifluoromethylphenyl)-7-oxo-                                 pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            63   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   7-thioxo-N--(2-trifluoromethylphenyl)-                                        pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            64   6,7-Dihydro-5,6-dimethyl-N--(5,6-dimethyl-                                    2-nitrophenyl)-3-methoxycarbonyl-7-thioxo-                                    pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            65   N--(2-Bromo-6-chlorophenyl)-6,7-dihydro-                                      5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                      pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            66   N--(2-Bromo-6-chloro-3-methylphenyl)-                                         6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   7-thioxopyrazolo[1,5-a][1,3,5]triazine-                                       2-sulphonamide                                                           67   N--(2-Bromo-6-chloro-5-methylphenyl)-                                         6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   7-thioxopyrazolo[1,5-a][1,3,5]triazine                                        2-sulphonamide                                                           68   N--(2-Dibromo-3-methylphenyl)-6,7-dihydro-                                    5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                      pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            69   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   N--(6-methyl-2-trifluoromethylphenyl)-7-thioxo-                               pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            70   N--(2-Difluoromethoxy-6-methylphenyl)-                                        6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   7-thioxopyrazolo[1,5-a][1,3,5]triazine-2-                                     sulphonamide                                                             71   6,7-Dihydro-5,6-dimethyl-N--(3,6-dimethyl-                                    2-nitrophenyl)-3-methoxycarbonyl-7-thioxo-                                    pyrazolo[1,5-a][1,3,5]triazine-2 sulphonamide                            72   N--[2,6-Bis(difluoromethoxyphenyl)]6-Bis(difluoromethoxyphenyl)]-6,7-         dihydro-                                                                      5,6-dimethyl-3-methoxycarbonyl-7-thioxo-                                      pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            73   6,7-Dihydro-5,6-dimethyl-N--(6-fluoro-                                        2-methoxycarbonyl-3-methylphenyl)-3-methoxy-                                  carbonyl-7-thioxopyrazolo[1,5-a][1,3,5]triazine                               2-sulphonamide                                                           74   6,7-Dihydro-5,6-dimethyl-3-methoxycarbonyl-                                   N--(2-methoxy-6-trifluoromethylphenyl)-7-thioxo-                              pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            75   N--(2-Bromo-6-methoxyphenyl)-6,7-dihydro-                                                                mp:                                                5,6-dimethyl-3-ethoxycarbonyl-7-thioxo-                                                                  210° C.                                     pyrazolo[1,5-a][1,3,5]triazine-2-sulphonamide                            76   3-Carbamoyl-N--(2-carboxy-6-methylphenyl)                                                                mp:257-                                            6,7-dihydro-5,6-dimethyl-7-oxopyrazolo-                                                                  258° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    77   3-Carbamoyl-N--(2-carboxy-6-methylphenyl)-                                                               mp:267-                                            6,7-dihydro-5,6-dimethyl-7-thioxopyrazolo-                                                               268° C.                                     [1,5-a][1,3,5]triazine-2-sulphonamide                                    ______________________________________                                    

The following examples illustrate the posibilties for areas of use ofthe compounds of the invention.

EXAMPLE A

Seeds of mono- and dicotyledenous plant species were sown in trays inhumus-containing sandy soil and covered with earth. The compounds of theinvention were applied as suspensions in 500 liters water/ha at a rateof 0.3 kg active ingredient/ha. to the soil surface before emergence ofthe plants.

After the treatment the test pots were put in a greenhouse and the testplants cultivated under good growing conditions. Three weeks after thetreatment plant damage was assessed. Untreated controls were used forcomparison.

As the table clearly shows numerous plant species weeds were destroyedor damaged. Wheat and barley were ressistant to the treatment.

In the following table:

    __________________________________________________________________________    Compounds of                                                                  invention                                                                             Tr                                                                              Ho                                                                              Br He                                                                              St Ab                                                                              Ma Vi                                                                              Ch So                                                                              Ec Se Ga                                      __________________________________________________________________________    Example 1                                                                             0 0 3  3 2  3 4  4 4  3 3  3 3                                        Example 2                                                                             2 2 3  3 2  2 4  3 3  4 4  3 3                                        Example 3                                                                             0 0 3  3 1  2 4  3 3  3 3  4 2                                        Example 4                                                                             1 0 3  3 3  3 4  3 3  3 3  4 4                                        Example 5                                                                             0 0 3  3 3  3 4  3 4  2 2  2 3                                        Example 6                                                                             0 1 2  3 3  2 4  4 4  3 3  2 4                                        Example 7                                                                             0 1 2  3 2  2 4  3 3  2 2  2 2                                        Example 8                                                                             1 2 3  3 2  2 4  3 4  4 3  4 3                                        Example 9                                                                             0 1 2  3 2  2 4  3 3  3 2  3 3                                        Example 10                                                                            1 1 3  3 3  2 4  3 3  3 3  2 3                                        Example 15                                                                            0 --                                                                              1  1 -- 0 4  0 -- --                                                                              -- 0 0                                        Example 16                                                                            1 --                                                                              1  2 -- 0 4  --                                                                              -- --                                                                              -- 1 2                                        Example 17                                                                            0 --                                                                              3  3 -- 3 4  --                                                                              -- --                                                                              -- 3 3                                        Example 18                                                                            0 --                                                                              3  3 -- 3 3  --                                                                              -- --                                                                              -- 2 2                                        Example 19                                                                            0 --                                                                              3  3 -- 3 4  --                                                                              -- --                                                                              -- 2 2                                        Example 20                                                                            0 --                                                                              3  2 -- 1 4  --                                                                              -- --                                                                              -- 0 2                                        Example 21                                                                            1 --                                                                              3  2 -- 1 4  --                                                                              -- --                                                                              -- 3 3                                        Example 22                                                                            0 --                                                                              -- --                                                                              -- 3 4  --                                                                              -- --                                                                              -- 4 4                                        Example 23                                                                            0 --                                                                              3  3 -- 3 4  --                                                                              -- --                                                                              -- 3 3                                        Example 24                                                                            0 --                                                                              0  0 -- 0 3  1 -- --                                                                              -- 0 0                                        Example 25                                                                            0 --                                                                              3  3 -- 2 4  --                                                                              -- --                                                                              -- 2 4                                        Example 26                                                                            0 --                                                                              3  2 -- 2 4  --                                                                              -- --                                                                              -- 0 2                                        Example 27                                                                            1 --                                                                              2  2 -- 1 4  --                                                                              -- --                                                                              -- 0 2                                        Example 28                                                                            0 --                                                                              2  1 -- 0 3  --                                                                              -- --                                                                              -- 0 3                                        Example 29                                                                            1 --                                                                              3  2 -- 0 4  --                                                                              -- --                                                                              -- 0 3                                        Example 30                                                                            0 --                                                                              -- --                                                                              -- 3 4  --                                                                              -- --                                                                              -- 4 4                                        Example 39                                                                            0 --                                                                              3  3 -- 0 4  --                                                                              -- --                                                                              -- 3 3                                        Example 42                                                                            1 --                                                                              3  3 -- 0 4  --                                                                              -- --                                                                              -- 3 3                                        Example 45                                                                            0 --                                                                              -- --                                                                              -- 0 2  --                                                                              -- --                                                                              -- 1 2                                        Example 46                                                                            0 --                                                                              -- --                                                                              -- 2 4  --                                                                              -- --                                                                              -- 2 3                                        Example 47                                                                            0 --                                                                              -- --                                                                              -- 0 3  --                                                                              -- --                                                                              -- 0 2                                        Example 48                                                                            0 --                                                                              -- --                                                                              -- 1 4  --                                                                              -- --                                                                              -- 2 4                                        Control 0 0 0  0 0  0 0  0 0  0 0  0 0                                        __________________________________________________________________________     0 = no activity                                                               4  total destruction of the plant.                                            Tr = Triticum aestivum                                                        Ho = Hordeum distichum                                                        Br = Brassica napus napus                                                     He = Helianthus annuus                                                        St = Stellaria media.                                                         Ab = Abutilon hybridum                                                        Ma = Matricaria chamomilla                                                    Vi = Viola tricolor                                                           Ch = Chrysanthemum segetum                                                    So = Sorghum sativum                                                          Ec = Echinochloa crusgalli                                                    Se = Setaria italica                                                          Ga =  Galium aparine                                                          -- = not tested                                                          

EXAMPLE B

Seeds of mono- and dicotyledenous plant species were sown in trays inhumus-containing sandy soil and covered with earth. The compounds of theinvention were applied as suspensions in 500 liters water/ha at a rateof 0.3 kg active ingredient/ha. to the soil surface after emergence ofthe plants.

After the treatment the test pots were put in a greenhouse and the testplants cultivated under good growing conditions. Two weeks after thetreatment plant damage was assessed. Untreated contols were used forcomparison.

As the table clearly shows numerous plant species weeds were destroyedor damaged. Wheat and barley were ressistant to the treatment.

In the following table:

    ______________________________________                                        Compounds                                                                                                  of                                                                            invention Tr Ho Br Ly Me He St Ab Ma Vi Ch Ga    ______________________________________                                        Example 1                                                                              0     0     3   4   3   3   4   2   3   2   3                                                     4                                                                             Example 2 1 0 3 3 3 3 4 2 3 3 3 3                                             Example 3 0 0 3 3 4 3 3 2 2 3 2 3                                             Example 4 1 2 4 4 3 4 4 2 3 1 4 4                                             Example 5 0 0 2 3 3 3 2 2 3 3 4 3                                             Example 6 0 0 3 4 3 4 3 2 4 2 4 4                                             Example 7 0 0 3 3 3 3 2 3 2 2 2 3                                             Example 8 0 2 3 3 3 3 4 3 3 2 4 4                                             Example 9 0 0 2 2 2 2 3 1 2 1 2 3                                             Example 10 0 0 2 3 2 3 3 2 2 2 3 3                                            Control 0 0 0 0 0 0 0 0 0 0 0 0                  ______________________________________                                         0 = no activity                                                               4  total destruction of the plant.                                            Tr = Triticum aestivum                                                        Ho = Hordeum distichum                                                        Br = Brassica napus napus                                                     Ly = Lycopersicon esculentum                                                  Me = Medicago sativa                                                          He = Helianthus annuus                                                        St = Stellaria media.                                                         Ab = AbutiIon hybridum                                                        Ma = Matricaria chamomilla                                                    Vi = Viola tricolor                                                           Ch = Chrysanthemum segetum                                                    Ga = Galium aparine                                                      

We claim:
 1. 6,7-Dihydropyrazole[1,5-a][1,3,5]triazine-2-sulphonamidesof formula I ##STR13## in which Ar is phenyl, naphthyl, pyridyl orthienyl group of general formula ##STR14## R₁, R₂, R₃, R₄ and R₅ are thesame or different and are hydrogen, a C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl orC₂ -C₆ -alkynyl group, each of which is optionally substituted by one ormore of the same or different halo, hydroxy, halo-C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, halo-C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinylor C₁ -C₄ -alkylsulphonyl, halogen, C₁ -C₄ -alkoxy, a group R₁₀ --O--CO,a carbamoyl group R₁₁ R₁₂ N--CO--, an amino group R₁₁ R₁₂ N--, cyano,nitro, a sulphur containing group R₁₀ --S(O)_(n) --, an acyl group R₁₀--CO, a group R₁₀ --O--CO--(CH₂)_(n), or phenyl or phenoxy, both ofwhich are optionally substituted by one of more of C₁ -C₄ -alkyl, haloor nitro,R₆ is hydrogen, an acyl group R₁₀ --CO, a group R₁₀ --O--CO--,C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkynyl, phenyl-C₁ -C₄ -alkyl, acarbamoyl group R₁₁ R₁₂ N--CO--, an alkali metal, an alkaline earthmetal or ammonium group, optionally substituted by C₁ -C₆ -alkyl, R₇ andR₈ are the same or different and are hydrogen, a C₁ -C₆ -alkyl, C₂ -C₆-alkenyl or C₂ -C₆ -alkynyl group, each of which is optionallysubstituted by halo or C₁ -C₄ -alkoxy, a phenyl-C₁ -C₆ -alkyl, phenyl-C₂-C₆ -alkenyl or phenyl-C₂ -C₆ -alkynyl group, each of which isoptionally substituted by halo, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl or halo-C₁ -C₄ -alkyl, phenyl, substituted by R₁,R₂, R₃, R₄ and R₅, an acyl group R₁₀ --CO, a group R₁₀ --O--CO, a groupR₁₀ --O--CO--(CH₂)_(n), a carbamoyl group R₁₁ R₁₂ N--CO--, or asulphonyl group R₁₀ --SO₂, R₉ is hydrogen, a C₁ -C₆ -alkyl, C₂ -C₆-alkenyl or C₂ -C₆ -alkynyl group, each of which is optionallysubstituted by halo or C₁ -C₄ -alkoxy, a phenyl-C₁ -C₆ -alkyl, phenyl-C₂-C₆ -alkenyl or phenyl-C₂ -C₆ -alkynyl group, each of which isoptionally substituted by halo, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl or halo-C₁ -C₄ -alkyl, phenyl, substituted by R₁,R₂, R₃, R₄ and R₅, an acyl group R₁₀ --CO, a group R₁₀ --O--CO, a groupR₁₀ --O--CO--(CH₂)_(n), a carbamoyl group R₁₁ R₁₂ N--CO--, a sulphonylgroup R₁₀ --SO₂ or R₁₀ --O--SO₂, cyano or nitro R₁₀ is hydrogen, a C₁-C₆ -alkyl, C₂ -C₆ -alkenyl, C₂ -C₆ -alkynyl or phenyl-C₁ -C₄ -alkylgroup, each of which is optionally substituted by one or more of thesame or different halo, hydroxy or C₁ -C₄ -alkoxy, or phenyl, optionallysubstituted by halo, nitro or C₁ -C₄ -alkyl, R₁₁ and R₁₂ are the same ordifferent and are hydrogen, a C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl or C₂ -C₆-alkynyl group, each of which is optionally substituted by one or moreof the same or different halo, hydroxy or C₁ -C₄ -alkoxy, or R₁₁ and R₁₂together with the adjacent nitrogen form a pyrrolidinyl, piperidino ormorpholino ring, X is oxygen or sulphur, and n is 0, 1 or
 2. 2.6,7-Dihydropyrazole[1,5-a][1,3,5]triazine-2-sulphonamides according toclaim 1, in which Ar is a phenyl group of general formula ##STR15## R₁and R₅ are the same or different and are halogen, methyl,trifluoromethyl, nitro, methoxy or methoxycarbonyl,R₂, R₃ and R₄ are thesame or different and are hydrogen, halogen, trifluoromethyl or a C₁ -C₄-alkyl group, R₆ is hydrogen, said metal or a C₁ -C₄ -acyl group, R₇ andR₈ are the same or different and are hydrogen, C₁ -C₄ -acyl, C₁ -C₆-alkyl, C₂ -C₄ -alkenyl or phenyl, and R₉ is hydrogen, a C₁ -C₄ -acylgroup, a group R₁₀ --O--CO, a carbamoyl group R₁₁ R₁₂ N--CO--, asulphonyl group R₁₀ --SO₂, cyano or nitro.
 3. A herbicidal andplant-growth regulant composition with comprises an effective herbicidaland plant growth regulant amount of a compound according to claim 1, inadmixture with carriers and diluents.
 4. A method of combating weedswhich comprises applying to the weeds or their locus an effectiveherbicidal amount of a compound according to claim
 1. 5. A method ofregulating the growth of plants which comprises applying to the plantsor their locus a plant growth regulant amount of a compound according toclaim
 1. 6. A herbicidal and plant-growth regulant composition whichcomprises a compound according to claim 2, in admixture with carriersand diluents.
 7. A method of combating weeds which comprises applying tothe weeds or their locus a compound according to claim
 2. 8. A method ofregulating the growth of plants which comprises applying to the plantsor their locus a plant growth regulant amount of a compound according toclaim
 2. 9. N-(2,6-disubstitutedphenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-pyrazolo[1,5-a][1,3,5]triazine-2-sulfonamideaccording to claim 2, in which the substituents are individuallyselected from the group consisting of halogen, methyl, nitro andmethoxy.
 10. N-(2,6-disubstitutedphenyl)-6,7-dihydro-5,6-dimethyl-3-methoxycarbonyl-pyrazolo[1,5-a][1,3,5]triazine-2-sulfonamideaccording to claim 9 in which said substituents are individuallyselected from the group consisting of chloro, fluoro and methyl and X isS.
 11. A method of regulating the growth of plants which comprisesapplying to the plants or their locus a plant growth regulant amount ofa compound according to claim
 9. 12. A method of regulating the growthof plants which comprises applying to the plants or their locus a plantgrowth regulant amount of a compound according to claim
 10. 13. A methodof combatting weeds which comprises applying to the weeds or their locusan effective herbicidal amount of a compound according to claim
 9. 14. Amethod of combatting weeds which comprises applying to the weeds ortheir locus an effective herbicidal amount of a compound according toclaim
 10. 15. A herbicidal and plant-growth regulant composition whichcomprises an effective herbicidal and plant growth regulant amount of acompound according to claim 9, in admixture with carriers and diluents.16. A herbicidal and plant-growth regulant composition which comprises acompound according to claim 10 in admixture with carriers and diluents.